EP0961805B1 - Composant pour la production de melanges polymeres a base d'amidon, et procede de production de ce composant - Google Patents

Composant pour la production de melanges polymeres a base d'amidon, et procede de production de ce composant Download PDF

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Publication number
EP0961805B1
EP0961805B1 EP98963360A EP98963360A EP0961805B1 EP 0961805 B1 EP0961805 B1 EP 0961805B1 EP 98963360 A EP98963360 A EP 98963360A EP 98963360 A EP98963360 A EP 98963360A EP 0961805 B1 EP0961805 B1 EP 0961805B1
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EP
European Patent Office
Prior art keywords
polyvinylacetate
component
added
starch
mass
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP98963360A
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German (de)
English (en)
Other versions
EP0961805A1 (fr
Inventor
Werner Berger
Lutz Jeromin
Uta Mierau
Guntram Opitz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Biop Biopolymer Technologies AG
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Biop Biopolymer Technologies AG
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Publication of EP0961805A1 publication Critical patent/EP0961805A1/fr
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Publication of EP0961805B1 publication Critical patent/EP0961805B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/02—Starch; Degradation products thereof, e.g. dextrin

Definitions

  • the invention relates to a component made of polyvinyl acetate and alkali water glass Production of thermoformable, good water-resistant, biological degradable and light-colored polymer mixtures based on starch, which are used to manufacture Films, semi-finished or finished products, e.g. for packaging, containers, gardening supplies, especially cultivation aids, and can be used otherwise and a method for Manufacturing the component.
  • thermoplastic starch alone or as a polymer mixture or polymer melt or Polymer blend (in the following polymer mixture) become known. This work was done with pursued the goal of new or expanded fields of application for renewable raw materials tap.
  • the use value of the extrudate and the products made from it is low.
  • the material is highly hydrophilic.
  • the starch plasticized with water and glycerol is included in the extruder mainly processed polyvinyl acetate to a polymer mixture.
  • the extrudate has opposite TPS better water resistance.
  • thermoplastic starch and a hydrophobic polymer for example polyvinyl acetate, of higher quality thermoplastically deformable, biodegradable polymer mixtures can be extruded, and a process for producing the component from polyvinyl acetate and alkali water glass specify.
  • the component is obtained in that the polyvinyl acetate in The presence of catalytic additives of low molecular weight, organic mono-, di- and Trihydroxyl compounds (e.g. methanol, ethanol, ethylene glycol, glycerol) below continuous addition of basic compounds and the alkali silicate in the Batch process is hydrolyzed and saponified.
  • catalytic additives of low molecular weight, organic mono-, di- and Trihydroxyl compounds e.g. methanol, ethanol, ethylene glycol, glycerol
  • the component contains organosilicates of great homogeneity and fineness from partially saponified Polyvinyl acetate and alkali silicate solution, further reaction products produced in situ and Remains of the catalyst used in its manufacture.
  • the component is solid at room temperature and a structured liquid above 40 ° C. After removal from the mixer, excess water can be removed by centrifugation become. A residual moisture of 25% to 30% usually remains in the product. Is in it the catalyst used is approximately proportional to the amounts used Catalyst / liquid included.
  • the various components are manufactured in a batch process Solid-liquid mixer from Gebrüder Lödige Maschinenbau GmbH.
  • the mixer is equipped with a centrifugal control that can be regulated via the speed (max. approx. 350 rpm) and a cutter head, operable at constant speed.
  • the heating takes place through the Double jacket of the mixer using a pressure-superimposed temperature control system or with direct steam.
  • reaction times After reaching the reaction temperature of 120 to 140 ° C, reaction times of 1 to 2 Hours required.
  • the degree of swelling (Q in%) and solubility (L in%) were determined on the test specimens, which were stored in water at room temperature for 24 hours.
  • the degree of swelling corresponds to the quotient of the mass difference between the undried, swollen test specimen (m Q ) and the same, dried test specimen before swelling (m A ) to the initial mass of the dry test specimen before swelling (m A ):
  • Q m Q - m A m A (in %)
  • the calcium hydroxide is weighed intimately into the polyvinyl acetate / glycerol mixture homogenized. The mixture is then brought to the reaction temperature and over 1 h leave. The soda water glass is then dosed as in Examples 1 and 2.
  • the degree of pre-saponification can be varied.
  • the reaction batch is 5% native potato starch, based on the weight of Polyvinyl acetate suspension, added before the hydrolysis and to that in Example 1 described way implemented. There is a certain difference compared to the values from Example 1 Deterioration on (table, example 4).
  • the reaction product of polyvinyl acetate, sodium hydroxide and Sodium water glass is 5% potato starch and 0.5% vinyl acetate, based on the weight added to the polyvinyl acetate suspension and a one-hour transesterification at 40 ° C. carried out.
  • the product properties improve significantly. (Table, example 5).
  • Another way of influencing the property profile of extruded starch / polyvinyl acetate mixtures is through the synthesis of a component consisting of the polyvinyl acetate suspension, in some cases saponified with calcium hydroxide, and sodium disilicate.
  • the composition of the reaction mixture is chosen so that it corresponds to the degree of saponification and silicate content of the component according to Example 1.
  • the polyvinyl acetate suspension, calcium hydroxide and sodium disilicate are weighed out, brought to the reaction temperature and kept at this temperature for a time (2 h) corresponding to the water glass dosage.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Biological Depolymerization Polymers (AREA)

Claims (17)

  1. Composant destiné à la préparation de mélanges polymères à partir d'amidon thermoplastifié et d'un polymère hydrophobe, par exemple de poly(acétate de vinyle), caractérisé en ce que le composant contient des organosilicates possédant une structure largement homogène de poly(acétate de vinyle) partiellement saponifié et d'une solution de silicate alcalin, d'autres produits de réaction fabriqués in situ et des restes du catalyseur utilisé pour la préparation, et est synthétisé dans une dispersion aqueuse basique en ajoutant un catalyseur de composés mono-, di- ou tri-hydroxyle organiques de faible masse moléculaire dans une quantité comprise entre 0,5 et 20 %, sur la base de la masse du poly(acétate de vinyle), lors d'un procédé discontinu.
  2. Procédé de préparation, d'un composant à partir de poly(acétate de vinyle) et de silicate alcalin, comme en particulier de verre soluble alcalin, par mélange intensif et cisaillement, à une température élevée et une pression élevée - pour fabriquer des mélanges polymères composés d'un amidon thermoplastifié et d'un polymère hydrophobe, comme en particulier du poly(acétate de vinyle), caractérisé en ce que le poly(acétate de vinyle) est hydrolysé et saponifié lors d'un procédé discontinu, en présence d'ajouts catalytiques d'une quantité de 0,5 à 20 %, sur la base de la masse du poly(acétate de vinyle), de composés mono-, di- ou tri-hydroxyle organiques de faible masse moléculaire, en ajoutant en continu des composés réagissant de façon basique et du silicate alcalin.
  3. Procédé selon la revendication 2, caractérisé en ce que le poly(acétate de vinyle) est pré-saponifié avec des composés réagissant de façon basique jusqu'à un degré d'hydrolyse compris entre 10 % et 30 %, puis saponifié de façon finale selon un degré d'hydrolyse compris entre 50 % et 80 %.
  4. Procédé selon la revendication 2, caractérisé en ce que, à partir du poly(acétate de vinyle) et du verre soluble, en partant d'une valeur de pH comprise entre 9 et 10, on élabore un organosilicate légèrement alcalin présentant une valeur de pH comprise entre 7 et 8,5.
  5. Procédé selon la revendication 2, caractérisé en ce que l'on ajoute un hydroxyde en même temps que le verre soluble alcalin ou avant.
  6. Procédé selon la revendication 2, caractérisé en ce que l'on ajoute au poly(acétate de vinyle) de l'hydroxyde de calcium jusqu'à atteindre un degré de saponification compris entre 10 % et 40 %.
  7. Procédé selon la revendication 2, caractérisé en ce que l'on ajoute en tant que catalyseur du méthanol et/ou de l'éthanol et/ou de l'éthylèneglycol et/ou du diéthylèneglycol et/ou du triéthylèneglycol et/ou du glycérol.
  8. Procédé selon la revendication 2, caractérisé en ce que la totalité des composés de catalyseur ajoutés ne dépasse pas une quantité comprise entre 5 % et 17 %, sur la base de la masse du polyacétate de vinyle.
  9. Procédé selon la revendication 8, caractérisé en ce que, dans le procédé de charge, le poly(acétate de vinyle) se présente sous la forme d'une suspension aqueuse, est chauffé à une température réactionnelle comprise entre 100 °C et 150 °C, le composé réagissant de façon basique est ajouté par dosage en continu pour la pré-saponification et, une fois atteint le degré de saponification souhaité, la solution de verre soluble alcalin est dosée à la température réactionnelle.
  10. Procédé selon la revendication 2, caractérisé en ce que le rapport de mélange entre poly(acétate de vinyle) et silicate alcalin, exprimé en fractions en masse de la matière solide, est compris dans la gamme allant de 50:50 à 80:20.
  11. Procédé selon la revendication 2, caractérisé en ce que, à la place de la solution de silicate alcalin, on utilise au moins en partie du disilicate de sodium et un hydroxyde.
  12. Procédé selon la revendication 2, caractérisé en ce que l'on ajoute à la préparation réactionnelle ou au composant du (3-glycidyloxypropyl)triméthoxysilane.
  13. Procédé selon la revendication 12, caractérisé en ce que la fraction en masse de silane est comprise entre 3 % et 15 % de la quantité de silicate incorporée avec la solution de silicate alcalin.
  14. Procédé selon la revendication 2, caractérisé en ce que l'on ajoute à la préparation réactionnelle ou au composant de l'amidon natif.
  15. Procédé selon la revendication 14, caractérisé en ce que l'on ajoute 5 % à 15 % d'amidon natif, sur la base de la masse du poly(acétate de vinyle).
  16. Procédé selon la revendication 14, caractérisé en ce que l'on ajoute avec l'amidon, de l'acétate de vinyle.
  17. Procédé selon la revendication 16, caractérisé en ce que l'on ajoute 0,5 à 1,5 % d'acétate de vinyle, sur la base de la masse du poly(acétate de vinyle).
EP98963360A 1997-11-17 1998-11-16 Composant pour la production de melanges polymeres a base d'amidon, et procede de production de ce composant Expired - Lifetime EP0961805B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19750846 1997-11-17
DE19750846A DE19750846C1 (de) 1997-11-17 1997-11-17 Verfahren zur Herstellung einer Komponente für die Herstellung von Polymermischungen auf der Basis von Stärke
PCT/DE1998/003385 WO1999025756A1 (fr) 1997-11-17 1998-11-16 Composant pour la production de melanges polymeres a base d'amidon, et procede de production de ce composant

Publications (2)

Publication Number Publication Date
EP0961805A1 EP0961805A1 (fr) 1999-12-08
EP0961805B1 true EP0961805B1 (fr) 2004-04-14

Family

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Family Applications (1)

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EP98963360A Expired - Lifetime EP0961805B1 (fr) 1997-11-17 1998-11-16 Composant pour la production de melanges polymeres a base d'amidon, et procede de production de ce composant

Country Status (6)

Country Link
US (1) US6958369B2 (fr)
EP (1) EP0961805B1 (fr)
AT (1) ATE264355T1 (fr)
DE (1) DE19750846C1 (fr)
DK (1) DK0961805T3 (fr)
WO (1) WO1999025756A1 (fr)

Families Citing this family (19)

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DE19938672C2 (de) * 1999-08-06 2001-11-22 Biop Biopolymer Gmbh Verfahren zur Herstellung einer thermoplastischen Polymermischung auf Stärkebasis durch reaktive Extrusion
US7402618B2 (en) * 2000-11-23 2008-07-22 Hao Xu Biodegradable composition for the preparation of tableware, drink container, mulching film and package and method for preparing the same
CN1121452C (zh) * 2000-11-23 2003-09-17 许浩 生物降解环保型餐具的配方及生产工艺
DE10062848C1 (de) 2000-12-11 2002-04-04 Biop Biopolymer Gmbh Wasserformbeständiges, thermoplastisches Stärkematerial, Verfahren zu dessen Herstellung und dessen Verwendung
EP1229075B2 (fr) 2001-02-01 2011-08-31 BIOP Biopolymer Technologies AG Procédé de préparation d'un composite de polymère thermoplastique à base d'amidon contenant des particules integrées nanoscopiques
JP2002363215A (ja) * 2001-05-25 2002-12-18 Biop Biopolymer Gmbh デンプンに基づくポリマー混合物を製造するための成分及びこの成分を製造する方法
DE10258227A1 (de) 2002-12-09 2004-07-15 Biop Biopolymer Technologies Ag Biologisch abbaubare Mehrschichtfolie
US20080036115A1 (en) * 2004-03-10 2008-02-14 Minoru Ueda Starch Resin Composition, Molded Product Using the Same and Method for Producing the Same
WO2006045295A2 (fr) * 2004-10-28 2006-05-04 Maiwald Beratung + Planung Procede de fabrication de granulats poreux et de melanges de granulats poreux et utilisation de ceux-ci dans la resolution de problemes ecologiques
US7931778B2 (en) 2005-11-04 2011-04-26 Cargill, Incorporated Lecithin-starches compositions, preparation thereof and paper products having oil and grease resistance, and/or release properties
US20070129467A1 (en) * 2005-12-02 2007-06-07 Frederic Scheer Bio based biodegradable polymer compositions and use of same
EP2855576B1 (fr) 2012-05-31 2021-06-30 Saudi Basic Industries Corporation Article étiré dans deux axes
US10457023B2 (en) 2013-11-14 2019-10-29 Saudi Basic Industries Corporation Bi-axially stretched article and silage film
EP3233531A1 (fr) * 2014-12-19 2017-10-25 Novamont S.p.A. Dérivés d'amidon déstructuré et compositions élastomères en contenant
US10400105B2 (en) 2015-06-19 2019-09-03 The Research Foundation For The State University Of New York Extruded starch-lignin foams
DE102017107539B4 (de) 2017-04-07 2021-07-22 Leibniz-Institut Für Polymerforschung Dresden E.V. Biobasierte schmelzklebstoffe und verfahren zu ihrer herstellung
US20210261309A1 (en) 2018-06-29 2021-08-26 Stichting Wageningen Research Dynamic modified atmosphere packaging material for fresh horticultural products
EP3632937B1 (fr) 2018-10-04 2022-04-13 Amelotec Ltd. Agent de liaison hydraulique pour polymères et son procédé de production
EP3699143A1 (fr) 2019-02-25 2020-08-26 United Biopolymers, S.A. Agent de compatibilité alcalin à liaison hydro sur la base de poly(alcool vinylique), son procédé de production et son utilisation

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Also Published As

Publication number Publication date
EP0961805A1 (fr) 1999-12-08
US20020061943A1 (en) 2002-05-23
WO1999025756A1 (fr) 1999-05-27
DE19750846C1 (de) 2000-01-27
ATE264355T1 (de) 2004-04-15
US6958369B2 (en) 2005-10-25
DK0961805T3 (da) 2004-08-02

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